Memory with high dielectric constant antifuses adapted for use at low voltage

ABSTRACT

A memory cell is provided that includes a diode and a resistance-switching material layer coupled in series with the diode. The resistance-switching material layer: (a) has a dielectric constant in the range of about 5 to about 27, and (b) includes a material from the family consisting of X v O w , wherein X represents an element from the family consisting of Hf and Zr, and wherein the subscripts v and w have non-zero values that form a stable compound. Other aspects are also provided.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.12/367,214, filed on Feb. 6, 2009, now U.S. Pat. No. 7,781,805, which isa continuation of U.S. patent application Ser. No. 11/173,973, filed onJul. 1, 2005, now abandoned, each of which is incorporated by referenceherein in its entirely for all purposes. This application relates toKnall U.S. patent application Ser. No. 11/174,234, titled “REVERSE-BIASMETHOD FOR WRITING MEMORY CELLS IN A MEMORY ARRAY,” filed on Jul. 1,2005, now U.S. Pat. No. 7,304,888, and to Cleeves U.S. patentapplication Ser. No. 11/174,240, titled “MEMORY CELL WITH HIGH-KANTIFUSE FOR REVERSE BIAS PROGRAMMING,” filed on Jul. 1, 2005, now U.S.Pat. No. 7,453,755, each of which and is incorporated herein byreference in its entirety for all purposes.

BACKGROUND

The invention relates to programming and reading an array of nonvolatilememory cells each comprising a diode in series with an antifuse.

Integrated circuit memories are typically large arrays of memory cellsconnected between bit lines and word lines. In order to achieve reliableprogramming and reading of the memory cells within the array, memorycells selected to be programmed or read must be isolated from memorycells that are not selected. Also, as it becomes increasingly importantto minimize power used by integrated circuit devices, it is desirable tominimize power consumption in integrated circuit memories. Lowering thevoltage for reading and writing usually reduces power consumption. Alsolowering the voltage usually allows elements of the integrated circuitdevice to shrink, thus reducing manufacturing cost. Therefore it isdesirable to program and operate memories at lower voltages.

FIG. 1 shows a representative portion of an integrated circuit memoryarray in which voltages have been applied in order to program one of thememory cells. Each of the memory cells comprises a diode in series withan antifuse connected between one of the word lines and one of the bitlines in the memory array. In FIG. 1, the cell selected to be programmedis at the intersection of word line WL4 and bit line BL2. In order toprogram this cell, a high voltage of 9 volts is applied to word line WL4and a ground voltage of 0 volts is applied to bit line BL2, thusapplying 9 volts to selected cell 4,2 at this intersection.

To avoid programming any of the other unselected cells, other bit linesreceive a voltage of 8.5 volts and other word lines receive 0.5 volts.This causes all unselected cells, for example cell 1,1 to receive areverse bias voltage (in the reverse direction of normal current flowthrough the diode) of −8.0 volts. Half-selected cells (in which eitherthe word line or the bit line receives a selected voltage) receive aforward bias voltage of 0.5 volts, which is less than the thresholdvoltage of the diodes, so only a small amount of current flows throughthe half-selected cells.

In order to avoid reverse bias breakdown, the diodes must bemanufactured so that they can tolerate the reverse bias of 8 volts, andthe antifuses must be manufactured to be somewhat leaky so that most ofthe voltage drop is across the diode and not the antifuse to assure thatthis relatively high voltage does not cause programming of the antifusein unselected cells. However, during programming, the reverse leakagethrough the unselected cells causes power drain. In a large array havingmany unselected memory cells, this power drain can be considerable.

For example, in a two-dimensional array of 1000×1000 memory cells, thereare one million memory cells. If only one row and one bit line areselected, there are 999×999 unselected cells all receiving an 8-voltbias, producing considerable power drain through the array. It isdesirable to minimize power drain, and particularly important tominimize power drain in battery operated applications. It is alsodesirable to shrink the area occupied by the memory array, therebyreducing cost.

Other materials besides silicon and silicon dioxide have been consideredfor making some integrated circuit structures. FIG. 2 a, taken fromMcPherson et al., “Proposed Universal Relationship Between DielectricBreakdown and Dielectric Constant,” IEDM December 2002 paper number26.6, shows measured values of dielectric constant and breakdownstrength for about 10 materials and shows that the correlationcoefficient between dielectric constant and breakdown strength is about0.81, which indicates a high correlation between the two parameters.

McPherson et al., “Trends in the Ultimate Breakdown Strength of HighDielectric-Constant Materials,” published in IEEE Transactions onElectron Devices, Vol. 50, No. 8, August 2003, indicates that theultimate breakdown strength E_(bd) of a dielectric material is found todecrease as the dielectric constant K increases. The paper indicatesthat great interest exists in the breakdown strength of high-Kdielectrics because for CMOS technology scaling to continue, theconventional SiO₂ gate-dielectric (which has a high E_(bd)) must bereplaced. The paper gives new time-dependent dielectric breakdown (TDDB)data over a wide range of dielectric materials. The paper also discussesacceleration factor (the relationship between voltage and time tobreakdown) and gives acceleration factor data for selected materials.But the McPherson et al. paper says nothing about materials used formaking antifuses or diodes such as are used for making memory cells.

FIG. 2 b, taken from the August 2003 McPherson paper, also examinesbreakdown strengths of four materials: silicon dioxide (SiO₂), hafniumsilicon oxynitride (HfSiON), tantalum oxide (Ta₂O₅), and PZT (a leadzirconate titanate ceramic), as a function of dielectric constant.(FIGS. 2 a and 2 b have a different appearance, but that is mainlybecause FIG. 2 a uses log-log scales and FIG. 2 b uses linear scales.)

SUMMARY

The present invention is defined by the appended claims, and nothing inthis section should be taken as a limitation on those claims.

In general, the invention is directed to methods of forming andprogramming an array of nonvolatile memory cells each comprising anantifuse in series with a diode. The invention takes advantage of theone-way nature of the diode and uses materials that allow for lowervoltage operation. In particular, antifuses having dielectric constantshigher than that of silicon dioxide and diodes having band gaps lowerthan that of silicon are found to be effective in allowing the memoriesto operate at lower voltages.

In order to shrink the memory cell horizontal area without havingmanufacturing problems, the vertical dimension of the memory cell mustalso be reduced, and that means the write voltage and read voltage mustbe reduced. But antifuses and diodes made from films of silicon dioxidehave already been made just a few atoms thick, and cannot be madethinner. However, using a material with a higher dielectric constantallows films of dielectric to be thicker for the same breakdown fieldstrength (breakdown voltage divided by thickness is breakdown fieldstrength).

One aspect of the invention is to form a memory cell from a diode inseries with an antifuse where the antifuse is made, not from silicondioxide, but from a material having a higher dielectric constant thansilicon dioxide. The elements lanthanum (La), hafnium (Hf), tantalum(Ta), yttrium (Y), zirconium (Zr), and niobium (Nb) when oxidized orcombined with nitrogen form dielectrics with higher dielectric constantsthan silicon dioxide and can each be used to form antifuses in memorycells that can be written and read at lower voltages than silicondioxide.

An aspect of the invention is to assure that the dielectric constant ofthe insulator used for the memory cell antifuse is higher than that ofsilicon dioxide (3.9). In particular, a dielectric constant range ofapproximately 5 to 27 in the antifuse and a band gap smaller than thatof silicon work well to produce memory cells that can be reliably readand written at lower voltages than memory cells of silicon dioxide andsilicon.

When the antifuse is formed from an insulator having a dielectricconstant above about 5 and the diode is a thin film with a band gapsmaller than silicon, the memory cells can be programmed by applying alow voltage in a direction opposite that of natural current flow throughthe diode, which shorts the antifuse to produce the programmed memorycell. A programming voltage sufficient to short the antifuse can belower than that required to program a memory cell made from a silicondioxide antifuse and a doped silicon diode. While a selected memory cellis being programmed, unselected memory cells preferably receive minimalvoltage, thus minimizing power consumption in the memory array.

It is also advantageous to program such a memory cell by applying twovoltages in the forward direction of the diode. The first application ofvoltage shorts the antifuse (forms a conductive path through theantifuse), and the second application of voltage makes a larger openingat the location of the short, thus reducing resistance to current flowthrough the short location.

It is important to avoid disturbing or programming unselected memorycells while programming the selected cells. It is also important toavoid disturbing any of the memory cells while reading the memory cells,and this is true for the life of the device, which may be on the orderof 10 years. A memory cell array is accessed by word lines and bitlines, typically running orthogonal to each other in separate horizontallayers of an integrated circuit structure, such that each memory cell isaccessed by one word line and one bit line.

The memory cells of the present invention each comprise an antifuse inseries with a diode. The antifuse may be placed at either the cathodeend or the anode end of the diode. According to one aspect of theinvention, while a voltage sufficient to short an antifuse is applied toa bit line contacting the selected memory cell and a ground voltage isapplied to a word line contacting the selected memory cell, a voltageless than or equal to the diode threshold voltage is applied to bitlines of unselected cells and a voltage that is lower than the voltagesufficient to short an antifuse of a memory cell by one diode thresholdvoltage is applied to word lines contacting unselected memory cells.This assures that the selected memory cell is programmed and thatunselected memory cells are not programmed or otherwise disturbed.

In a first aspect of the invention, a memory cell is provided thatincludes a diode and a resistance-switching material layer coupled inseries with the diode. The resistance-switching material layer: (a) hasa dielectric constant in the range of about 5 to about 27, and (b)includes a material from the family consisting of X_(v)O_(w), wherein Xrepresents an element from the family consisting of Hf and Zr, andwherein the subscripts v and w have non-zero values that form a stablecompound.

In a second aspect of the invention, a memory cell is provided thatincludes a diode and a resistance-switching material layer coupled inseries with the diode. The diode has a band gap smaller than that ofsilicon. The resistance-switching material layer: (a) has a dielectricconstant in the range of about 5 to about 27, and (b) includes amaterial from the family consisting of X_(v)O_(w), wherein X representsan element from the family consisting of Hf and Zr, and wherein thesubscripts v and w have non-zero values that form a stable compound.

In a third aspect of the invention, a memory cell is provided thatincludes a diode and a dielectric material layer coupled in series withthe diode. The diode has a band gap smaller than that of silicon. Thedielectric material layer: (a) has a dielectric constant in the range ofabout 5 to about 27, and (b) includes a material from the familyconsisting of X_(v)O_(w), wherein X represents an element from thefamily consisting of Hf and Zr, and wherein the subscripts v and w havenon-zero values that form a stable compound.

Other features and aspects of the present invention will become morefully apparent from the following detailed description, the appendedclaims and the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

Features of the present invention can be more clearly understood fromthe following detailed description considered in conjunction with thefollowing drawings, in which the same reference numerals denote the sameelements throughout.

FIG. 1 is a memory array showing prior art programming voltages.

FIG. 2 a shows breakdown strength as a function of dielectric constantfor a range of materials usable in semiconductor devices.

FIG. 2 b shows another curve of breakdown strength as a function ofdielectric constant.

FIGS. 3 a and 3 b shows an exemplary physical structure of memory cellelements comprising a diode plus an antifuse in a three-dimensionalarray.

FIG. 4 shows voltage versus current curves for some programmed andunprogrammed memory cells in exemplary devices.

FIG. 5 shows voltage versus current curves similar to those of FIG. 4but in which the height of a memory cell has been reduced.

FIG. 6 shows four curves of acceleration factor, which istime-to-breakdown as a function of electric field strength.

FIG. 7 shows a table of dielectric constant, acceleration factor, andbreakdown strength for several materials usable in the manufacture ofintegrated circuit memory arrays.

FIG. 8 shows voltages that can be used for programming memory cellsaccording to the invention.

FIG. 9 shows voltages that can be used for reading memory cellsaccording to the invention.

FIG. 10 shows voltages that can be used for writing memory cells withreverse bias, according to another embodiment of the invention.

DETAILED DESCRIPTION

When developing improvements in integrated circuit memories, it isdesirable to reduce the cost of manufacturing while improving operatingspeed, reducing power consumption, and maintaining a good usefullifetime of the devices. The present invention is directed to memoryarrays in which memory cells are formed from a diode and an antifuseconnected in series. Preferred embodiments orient the diode and antifusein a vertical stack between word lines and bit lines.

A critical requirement for shrinking memory devices to deep submicronsizes is to reduce the voltage levels required to write and read thememory cells. For example, whereas the prior art programming voltageillustrated in FIG. 1 is about 9 volts, the present invention will allowprogramming in the range of 3 to 5 volts. Read voltage can similarly bereduced to about 1 to 1.5 volts. Reducing the required read and writevoltages of the memory cells also allows shorter channel length CMOSdevices to be used in support circuits. When the write voltage isreduced in the diode-plus-antifuse memory cells of the invention, thelength of the intrinsic or lightly doped region between the heavilydoped n+ and p+ portions of the diode can be reduced. Thus, a shortervertical diode can be used in the memory cell. The horizontal spacingbetween memory cells can be reduced as the vertical diode is reduced inheight, which further reduces the area of the memory array. This areareduction and voltage reduction reduces cost and power consumption. Thelower write voltage is particularly important for thediode-plus-antifuse memory cells of this invention because leakagecurrents in the large number of unselected memory cells iscorrespondingly reduced by reducing voltage applied to the unselectedcells.

Careful attention to several parameters of materials used in the memorycells is especially important to reduce the write and read voltagesapplied to diode-plus-antifuse memory arrays and especially formonolithic three-dimensional memory arrays. A monolithic threedimensional memory array is one in which multiple memory levels areformed above a single substrate, such as a wafer, with no interveningsubstrates. The layers forming one memory level are deposited or growndirectly over the layers of an existing level or levels. In contrast,stacked memories have been constructed by forming memory levels onseparate substrates and adhering the memory levels atop each other, asin Leedy, U.S. Pat. No. 5,915,167, “THREE DIMENSIONAL STRUCTURE MEMORY.”The substrates of stacked memories may be thinned or removed from thememory levels before bonding, but since the memory levels are initiallyformed over separate substrates, such memories are not true monolithicthree dimensional memory arrays.

FIGS. 3 a and 3 b illustrate the structure of two embodiments of theinvention. The diode is made up of a P layer on top of an N− layer ontop of an N+ layer. In FIG. 3 a, this diode sits on an antifuse, whichsits on a word line WL. A bit line runs horizontally in a firstdirection above the diode structure. The word line WL runs horizontallyin a second direction below the antifuse structure. Thus, the antifuseis at the cathode end of the diode and is positioned between the cathodeend of the diode and the cathode end of the entire memory cell.

In FIG. 3 b, the structure is similar except that the P layer of thediode is adjacent the antifuse and therefore the antifuse is between theanode end of the diode and the anode end of the memory cell. In anotherembodiment not shown, the antifuse is positioned between the P layer ofthe diode and the N layers of the diode. The invention can incorporateany desired diode plus antifuse arrangement. The memory cell will bedescribed as having a cathode end and an anode end even though anantifuse may be between the end of the diode and the end of the memorycell. Further information about manufacturing diodes useful with thepresent invention can be found in:

-   -   Herner et al. U.S. patent application Ser. No. 11/125,606,        titled “HIGH-DENSITY NONVOLATILE MEMORY ARRAY FABRICATED AT LOW        TEMPERATURE COMPRISING SEMICONDUCTOR DIODES,” filed May 9, 2005;        and    -   Herner et al. U.S. patent application Ser. No. 10/954,577,        titled “JUNCTION DIODE COMPRISING VARYING SEMICONDUCTOR        COMPOSITIONS,” filed Sep. 29, 2004, now U.S. Pat. No. 7,224,013.

Suitable memory cell structures and configurations useful forcross-point antifuse arrays include, without limitation, those describedin the following enumerated disclosures, each of which is incorporatedherein by reference in its entirety:

-   -   Johnson et al. U.S. Pat. No. 6,034,882, titled “VERTICALLY        STACKED FIELD PROGRAMMABLE NONVOLATILE MEMORY AND METHOD OF        FABRICATION;”    -   Knall et al. U.S. Pat. No. 6,420,215, titled “THREE-DIMENSIONAL        MEMORY ARRAY AND METHOD OF FABRICATION;”    -   Johnson U.S. Pat. No. 6,525,953, titled “VERTICALLY-STACKED,        FIELD PROGRAMMABLE NONVOLATILE MEMORY AND METHOD OF        FABRICATION;”    -   Cleeves U.S. patent application Ser. No. 10/185,508, filed Jun.        27, 2002, titled “THREE DIMENSIONAL MEMORY,” now U.S. Pat. No.        7,081,377;    -   Herner et al. U.S. patent application Ser. No. 10/326,470, filed        Dec. 19, 2002, titled “AN IMPROVED METHOD FOR MAKING A HIGH        DENSITY NONVOLATILE MEMORY,” now abandoned; and    -   Herner et al. U.S. patent application Ser. No. 11/015,824,        titled “NONVOLATILE MEMORY CELL COMPRISING A REDUCED HEIGHT        VERTICAL DIODE,” filed Dec. 17, 2004, now U.S. Pat. No.        7,285,464.

FIGS. 4 and 5 show voltage versus current curves for exemplary devices.FIG. 4 shows the current to voltage characteristic curves of are-crystallized silicon diode-plus-antifuse memory cell incorporating avertical diode with a height of 350 nanometers. FIG. 5 shows thecharacteristic curves of a similar cell incorporating a vertical diodewith a height of 220 nanometers. The invention is envisioned with diodesthat are even shorter. Some embodiments of the invention incorporate lowband gap materials such as a silicon germanium alloy or even a puregermanium semiconductor as the low band gap material. Examples of suchdiodes for incorporation in the memory cell are described in more detailin the following references, each of which is incorporated in itsentirety herein by reference:

-   -   Herner et al. U.S. patent application Ser. No. 10/326,470,        supra;    -   Petti et al. U.S. patent application Ser. No. 10/728,230,        “SEMICONDUCTOR DEVICE INCLUDING JUNCTION DIODE CONTACTING        CONTACT-ANTIFUSE UNIT COMPRISING SILICIDE,” filed Dec. 3, 2003,        now U.S. Pat. No. 6,946,719; and

Herner, et al., U.S. patent application Ser. No. 10/954,577, “JUNCTIONDIODE COMPRISING VARYING SEMICONDUCTOR COMPOSITIONS,” filed Sep. 29,2004, now U.S. Pat. No. 7,224,013.

It is desirable to reduce the height of vertical memory cell structuresin order to reduce gaps formed as the structures are being patterned andfilled with a dielectric. Deep gaps are difficult to fill withoutleaving voids that can cause manufacturing and reliability problems. Themaximum aspect ratio that can be used without defects is determined bythe manufacturing equipment. Thus, using a tall memory cell limitsreducing the spacing between memory cells and thereby the density of thememory cells.

In one embodiment, this invention incorporates shorter vertical diodesdescribed in previously listed U.S. patent application Ser. No.11/015,824. However, in this previous structure, an unintendedprogramming problem may occur. As shown in FIG. 4, for the memory cellwith a 350 nanometer diode, an unprogrammed memory cell exhibits acurrent versus voltage curve indicated by short dashed lines and labeled“Unprogrammed.” For the reverse biased direction shown at the left sideof the figure, current remains small until voltage in the reversedirection exceeds about 10 volts. Thus, unprogrammed memory cells willnot carry large current when a reverse bias is applied at voltages belowabout 10 volts. This is important when programming voltages indicated byFIG. 1 are applied, since the large number of unselected cells allexperience a relatively large reverse bias of about 8 volts.

Returning to FIG. 4, when some of the memory cells have been programmed(their antifuses have been shorted), their voltage versus current curvesare indicated by long dashed lines labeled “Programmed.” The reversebias current rises sharply at about 10 volts but may still be acceptableat a reverse bias of 8 volts. However, the curves of FIG. 5 for memorycells with a 250 nanometer thick diode show a less favorable picture.Reverse bias current is high but possibly acceptable for unprogrammedcells, but for programmed cells, indicated by the long dashed lineslabeled “Programmed,” current rises sharply at a reverse bias of about 8volts, and a large number of previously programmed cells will cause thememory array to experience an unacceptable current during attempts toprogram other cells. Because of this, it is unacceptable to provide andprogram memory cells having short silicon diodes and silicon dioxideantifuses that must receive the programming voltages indicated in FIG.1.

One solution to this problem has been discussed in Knall U.S. Pat. No.7,304,888, titled “REVERSE-BIAS METHOD FOR WRITING MEMORY CELLS IN AMEMORY ARRAY.” That patent application previously has been incorporatedherein by reference. Another solution to the problem is to replace thesilicon and silicon dioxide materials used in the antifuses and diodeswith different materials having different breakdown strengths, differentthicknesses, different dielectric constants, different accelerationfactors (see below) and different band gaps.

Breakdown Strength

In order to program at lower voltage without making the antifuse toothin, the antifuse material must have a lower breakdown strength at anadequate thickness. Recent measurements of breakdown strength (theelectric field strength at which the dielectric develops a sudden andsustained rise in leakage current) as a function of dielectric constantsof materials have shown that there is a negative correlation betweenbreakdown strength E_(bd) and dielectric constant K. Silicon dioxide(SiO₂) has a dielectric constant of 3.9 and a breakdown strength ofabout 13 MV/cm (megavolts per centimeter). Higher-K dielectrics breakdown at lower field strengths, and therefore lower voltages for the samethickness. For optimum benefit, some embodiments incorporate acombination of changes. For antifuses, a material with a higherdielectric constant than silicon dioxide is used at a greater thicknessthan commonly used for silicon dioxide antifuses such that the change indielectric constant is greater than the change in thickness. Hence alower breakdown voltage is achieved along with greater manufacturingability for the antifuse.

Antifuse Thickness

It is desirable to make antifuses with a thickness greater than 20angstroms. If antifuse thickness becomes less than 20 angstroms (only afew atoms thick), rather than simply breaking down at a correspondinglylower voltage, another phenomenon occurs. Below about 20 angstroms, uponapplication of a voltage, the dielectric exhibits high tunneling currentwithout breaking down, such that it is difficult to form a permanentconductive path. An antifuse should behave as an insulator until abreakdown voltage is reached, then develop a permanent conductive pathdue to melting in the presence of high current that occurs uponbreakdown. Therefore it is desirable to use antifuse materials that havesufficiently high dielectric constants that they can be made thickerthan 20 angstroms and still break down cleanly at a fairly low voltage.

Making the antifuse too thick also has problems. Increased thicknessincreases resistance (reduces leakage) through the antifuse to the pointthat voltage drop across the memory cell (antifuse plus diode) is almostentirely across the antifuse, and the diode no longer protects theantifuse sufficiently from being shorted when a reverse bias is appliedto the memory cell. Therefore, it is undesirable to use antifusematerials that have such a high dielectric constant that they must bemade thicker than about 65 angstroms. We have found that a thicknessrange of 20 to 65 angstroms avoids both these problems.

Antifuse Materials

Some of the materials indicated in FIG. 2 a have dielectric constantsappropriate for antifuse manufacture. It is desirable to use a materialwith dielectric constant more than about 5 and less than about 27. Ifthe dielectric constant is much lower than 5 (as with silicon dioxide),the voltage needed to break down the thinnest practical antifuse will betoo high to allow the low voltage operation that accompanies furthershrinkage-of the memory array. If the dielectric constant is much higherthan 27, the leakage is too large to maintain a long read lifetime, orthe material must be too thick to break and form a low resistance paththrough the memory cell. Also, a thickness greater than about 65angstroms interferes with a good aspect ratio for maintaining good stepcoverage during manufacturing. Thus materials used in the invention havea dielectric constant between about 5 and about 27. Materials used inthe invention are manufactured to have a thickness of 20 to 65angstroms.

Materials that appear satisfactory for making antifuses programmable atlower voltages can be described with the general formulasX_(v)Si_(w)O_(x), X_(v)O_(w) and X_(v)Si_(w)O_(x)N_(y), where Xrepresents an element from the family consisting of lanthanum (La),hafnium (Hf), tantalum (Ta), yttrium (Y), zirconium (Zr), and niobium(Nb) and the subscripts v, w, x, and y can have any value that forms astable compound. Thus, some acceptable materials include HfO₂, La₂O₃,LaSiON, Hf₂SiO, HfSiON, Ta₂O₅, Ta₂O₃N to name a few.

Acceleration Factor

For both easy writing and undisturbed reading, it is desirable to have amaterial that sharply changes its behavior in response to changing theapplied voltage. That is, when being written at a WRITE voltage, thematerial should break down and change states quickly, for example over aperiod of microseconds or less in order for the memory cell to bewritten. However, when being read at a somewhat lower READ voltage, thematerial should reliably not break down even over an extended lifetimeon the order of 10 years.

Thus, for a desirable material, a curve that relates time to breakdownto voltage should have a steep slope. This slope is called accelerationfactor. We have recognized that a high acceleration factor is beneficialin the manufacture and operation of integrated circuit memory cells thatuse antifuses. Thus we have examined materials looking for highacceleration factors, thinking such materials could be used to makeantifuses and diodes in memory cells.

As presented in the above McPherson et al. paper, the characteristicbreakdown strengths E_(bd) of SiO₂, HfSiON, Ta₂O₅, and PZT are 13.6, 7,4, and 0.8 MV/cm, respectively. However, even though the breakdownstrength E_(bd) is observed to decrease with dielectric constant K, thefield acceleration factor γ is observed to increase with K. We see thatE_(bd) decreases as approximately K^(−0.65), while γ increases asK^(0.66). For high-K materials, the field acceleration factor γ issignificantly greater than that for SiO₂.

Desirable Antifuse Characteristics

FIG. 6 shows empirical results for four materials described in theMcPherson et al. paper, including silicon dioxide for comparison.Silicon dioxide has an acceleration factor γ of 3.5 cm/MV. This meansthat time to breakdown decreases moderately as voltage is increased. Butin order to achieve a sufficiently short write delay, a very high writefield strength (off the scale of FIG. 6) must be applied. To achievethis high field strength, the programming voltage must be very large,even when the silicon dioxide antifuse is made as thin as feasible inmanufacturing. For the thinnest feasible silicon dioxide thickness, theminimum write voltage for reasonable write performance is about 7 volts,which is higher than desired for scaling the memory array supportcircuits below a 300 nanometer gate length.

Other materials give improved results. Other materials have a higherdependence on voltage, as indicated by the steeper curves. The nextcurve in FIG. 6 is for hafnium silicon oxynitride, HfSiON. This materialhas a steeper acceleration factor γ of 6.5 cm/MV and a breakdown fieldstrength E_(bd) of 7 MV/cm. The steepness of the HfSiON curve means thatwriting can be done quickly at a 38 angstrom thickness, and reading maybe done at 1.5 volts, which leaves a lifetime of the memory cells in theacceptable 10-year range.

The acceleration factor curves of FIG. 6 suggest a method that can beused to select materials with optimum antifuse characteristics regardingthickness and dielectric constant that satisfy requirements for lifetimeand operating voltage in an antifuse memory array. Because of thestraight line shape of the acceleration factor curves and the inverseexponential relationship between E_(bd) and γ, as described above, allthe lines in FIG. 6 will converge at a point far above the data rangeshown. The line equations all have the form “y=mx+b”, where the slope“m” depends on K but not thickness, and the intercepts “b” are all thesame. The desired read lifetime and write lifetime are labeled onhorizontal lines in FIG. 6.

There are similar lines for other materials that extend from theintercept b through the read lifetime to the write lifetime. For each ofthese materials, the ratio of field strength E at the read lifetime tofield strength E at the write lifetime is about 46%. One aspect of thepresent invention is to use a read voltage that is less than about 46%of the write voltage. In one embodiment, the read voltage is between 0.8volts and 1.5 volts. A material is chosen that has a dielectric constantin the range of 5 to 27. Setting the read field strength to be 46% ofthe write field strength determines an optimum thickness. For thematerial HfSiON, for example, the read field strength can be seen to be4 MV/cm, which establishes an antifuse thickness of 38 angstroms for aread voltage of 1.5 volts.

Similarly, if tantalum oxide Ta₂O₅ at the high end of the desired Krange, is selected, the desired read field strength is 2.4 MV/cm, and athickness of 63 angstroms, at the top end of the desired thickness rangeis needed in order to assure the 10-year lifetime during reading. Butanther material, PZT, has such a steep acceleration curve and breaksdown at such low field strength that this material would have to be 400angstroms thick to be read at 1.5 volts over a long lifetime, so PZT isnot practical for antifuses in memory cells that will be read at 1.5volts. Of course, the same methodology can be used to choose a materialand an optimum thickness and dielectric constant if a higher or lowerread voltage is desired. For a higher or lower read voltage, the optimummaterial would have a correspondingly lower or higher dielectricconstant.

Additional materials are practical for antifuse use. FIG. 7 shows atable of characteristics of some materials being considered for use inmemories. In particular, the elements lanthanum (La), hafnium (Hf),tantalum (Ta), yttrium (Y), zirconium (Zr), praseodymium (Pr), titanium(Ti), and niobium (Nb) can all form oxides (La₂O₃, HfO₂, Ta₂O₅, Y₂O₃,ZrO₂, Pr₂O₃, TiO₂, Nb₂O₅) having higher dielectric constants and lowerbreaking strength than silicon dioxide (SiO₂). Other compounds andalloys, in particular, HfON, are also beneficial. Silicon has been foundto improve temperature stability on transition metal oxides, and can bepartially substituted for the transition metals. In this case, the ratioof the metal to silicon can be varied over a wide range.

Lower Band Gap Materials for Diodes

When considering materials for the diode of the memory cell, the bandgap of the diode material must be considered. It is a further aspect ofthe invention that the read voltage is reduced by using a low band gapsemiconductor material to form the diode. Band gap is an intrinsicproperty of a material, and determines the threshold voltage of thediode and to some extent the conductivity through the diode. The bandgap of silicon is about 1.12 electron volts at 300 degrees Kelvin.

The read voltage using re-crystallized silicon diodes has been about 2volts. At lower sensing currents, the read voltage for a silicon diodecould drop a few hundred millivolts, but it is difficult to form asilicon diode that can be read reliably at 1.5 volts. It is desirable toform the diodes from a material with a lower band gap than that ofsilicon so that programming of antifuses in series with the diodes maybe done more quickly and at lower programming voltages. Lifetime of theantifuses in the array is especially improved by using a lower readvoltage because for the one-time-programmable memory cells of thisinvention, far more of the lifetime is spent in read operations.

One group of materials that works well for diodes is the groupconsisting of germanium and the silicon germanium alloys. The diodes maybe formed either by re-crystallizing or by depositing the selected diodematerial. The general formula Si_(x)Ge_(1-x) encompasses this family ofmaterials (though elemental silicon is not included). As germaniumcontent increases, the band gap decreases proportionally to 0.66electron volts for pure germanium. So pure germanium has about half thediode threshold voltage of pure silicon. This Si_(x)Ge_(1-x) family isuseful for reducing the required read voltage while retaining adequatecurrent, and allows read voltage to be reduced by half a volt or more.Gallium antimony has a band gap of 0.72 electron volts and is alsosuitable for diodes. Indium arsenic at 0.36 electron volts and leadsulfide at 0.41 electron volts can provide even lower acceptable readvoltages.

Programming and Reading

With the new materials discussed above, it is possible to quicklyprogram (write) memory cells using forward diode bias voltages to thememory cells that are lower than used in the prior art. It is alsopossible to read the memory cells without disturbing their values over along lifetime, expected to be on the order of 10 years.

FIG. 8 shows application of voltages for writing a selected memory cell.It is easy to see by comparing FIG. 8 to FIG. 1 that all voltage levelsare lower. By selecting thickness and dielectric constant of the diodesand antifuses, the back bias voltages across the memory cells (in FIG.8, −4 volts) can be predominantly across the diode of the memory cell,especially if the antifuse has been previously programmed, so that nounintended programming occurs. In one embodiment, two successiveprogramming voltages are applied. The first voltage shorts the antifuseto form a conductive path and the second voltage causes current to passthrough the shorted antifuse and further reduces resistance of theshorted antifuse.

In one embodiment, the first voltage is chosen to provide the desiredwrite field and the subsequent current through the antifuse is not wellcontrolled due to the very sudden pop event. The second voltage is abouttwo volts higher at the array line driver, and is provided through acurrent limiting circuit such as any well know current mirror circuit.The current limit is adjusted to give a useful range of programmed cellresistance values, but the voltage at each memory cell is less wellcontrolled due to variation in location along the array lines, whichhave inherent resistance drops.

FIG. 9 shows application of voltages for reading a selected memory cell.As can be seen in FIG. 9, the selected cell receives a forward readvoltage of 1.5 volts, the half-selected cells receive zero volts, andthe unselected cells receive a reverse bias of −1.5 volts. Thesevoltages are low enough that no programming of unselected orhalf-selected cells occurs, and yet voltage to the selected cell (whichmay be a row or multi-layer stack of selected cells) is sufficient todetermine the state of the antifuse in the selected cell.

In one embodiment using an antifuse material of hafnium siliconoxynitride in a layer 38 angstroms thick, the READ voltage applied tothe selected cell is 1.5 volts. If the cell has been programmed, currentflowing from the word line WL4 to bit line BL2 is about 1 microamp,while if the cell has not been programmed, the current is about 1nanoamp. Thus the state of this memory cell can be observed. Reversebias voltage applied to unselected cells is −1.5 volts, which is lowenough to produce negligible leakage current. Bias to half-selectedcells is 0 volts, which produces no current.

In another embodiment not shown, the diodes are reversed to connect theanodes to the bit lines. During reading, the selected word line is atground voltage, the selected bit line is current-sensed and clamped at avoltage of 1.5 volts. The unselected word lines are at 1.5 volts, andthe unselected bit lines are at ground voltage. Thus all cellsexperience the same voltage drop as those shown in FIG. 9.

FIG. 10 shows another application of voltages for writing a selectedmemory cell. In FIG. 10, voltages are applied to reverse bias theselected cell. The biasing arrangement of FIG. 10 experiences very lowleakage because all unselected cells receive zero bias. The benefits ofreverse biasing are further described in Knall, U.S. patent applicationSer. No. 11/174,234. The smaller voltage values of FIG. 10, however, areachieved by using the materials discussed above.

Thus the selection of new materials discussed above allows programmingand reading at lower voltages than the prior art. Because the devicescan be scaled to smaller dimensions, both power and cost ofmanufacturing are reduced.

A word line arrangement having multiple layers of word line segments forthree-dimensional memory arrays may be used with memory cells of thepresent invention. Such a word line arrangement is described in detailin Scheuerlein U.S. patent application Ser. No. 10/403,844, now U.S.Pat. No. 6,879,505, which is incorporated herein by reference in itsentirety. A method for sensing while programming a non-volatile memorycell described by Kleveland et al. U.S. Pat. No. 6,574,145, may be usedwith the present invention for sensing memory cell values, and isincorporated herein by reference in its entirety.

The foregoing detail has described only a few of the many possibleimplementations of the present invention. For this reason, this detaileddescription is intended to illustrate, not to limit. Variations andmodifications of the embodiments disclosed herein may be made based onthe description set forth herein, without departing from the scope andspirit of the invention. It is only the following claims, including allequivalents, that are intended to define the scope of this invention.

Although certain embodiments have been described in the context of athree-dimensional, field-programmable, memory array, it should beappreciated that such an array is not necessarily required. Moreover,the embodiments described above are specifically contemplated to be usedalone as well as in various combinations. Accordingly, otherembodiments, variations, and improvements not described herein are notnecessarily excluded from the scope of the invention.

1. A memory cell comprising: a diode; and a resistance-switchingmaterial layer coupled in series with the diode, wherein theresistance-switching material layer: (a) has a dielectric constant inthe range of about 5 to about 27, (b) comprises a material from thefamily consisting of X_(v)O_(w), wherein X represents an element fromthe family consisting of Hf and Zr, and wherein the subscripts v and whave non-zero values that form a stable compound, and (c) has athickness between 20 and 65 angstroms.
 2. The memory cell of claim 1,wherein the diode comprises a band gap smaller than 1.12 electron volts.3. The memory cell of claim 1, wherein the diode comprises one or moreof germanium (Ge) and a silicon germanium alloy (Si_(x)Ge_(1-x)).
 4. Thememory cell of claim 1, wherein the resistance-switching material layercomprises HfO₂ or ZrO₂.
 5. The memory cell of claim 1, wherein thememory cell is adapted to be programmed with a voltage less than about 5volts.
 6. The memory cell of claim 1, wherein the diode comprisesre-crystallized material.
 7. The memory cell of claim 1, wherein thediode is formed from deposited material.
 8. The memory cell of claim 1,wherein the diode is adapted to be read using a bias voltage less thanabout 2 volts.
 9. The memory cell of claim 1, wherein the memory cellcomprises an array of such memory cells.
 10. The memory cell of claim 9,wherein the array of memory cells comprises a monolithic 3-dimensionalarray.
 11. A memory cell comprising: a diode comprising a semiconductormaterial with a band gap smaller than that of silicon; and aresistance-switching material layer coupled in series with the diode,wherein the resistance-switching material layer: (a) has a dielectricconstant in the range of about 5 to about 27, (b) comprises a materialfrom the family consisting of X_(v)O_(w), wherein X represents anelement from the family consisting of Hf and Zr, and wherein thesubscripts v and w have non-zero values that form a stable compound, and(c) has a thickness between 20 and 65 angstroms.
 12. The memory cell ofclaim 11, wherein the band gap is smaller than 1.12 electron volts. 13.The memory cell of claim 11, wherein the diode comprises one or more ofgermanium (Ge) and a silicon germanium alloy (Si_(x)Ge_(1-x)).
 14. Thememory cell of claim 11, wherein the resistance-switching material layercomprises HfO₂ or ZrO₂.
 15. The memory cell of claim 11, wherein thememory cell is adapted to be programmed with a voltage less than about 5volts.
 16. The memory cell of claim 11, wherein the diode comprisesre-crystallized material.
 17. The memory cell of claim 11, wherein thediode is formed from deposited material.
 18. The memory cell of claim11, wherein the diode is adapted to be read using a bias voltage lessthan about 2 volts.
 19. The memory cell of claim 11, wherein the memorycell comprises an array of such memory cells.
 20. The memory cell ofclaim 19, wherein the array of memory cells comprises a monolithic3-dimensional array.
 21. A memory cell comprising: a diode comprising asemiconductor material with a band gap smaller than that of silicon; anda dielectric material layer coupled in series with the diode, whereinthe dielectric material layer: (a) has a dielectric constant in therange of about 5 to about 27, (b) comprises a material from the familyconsisting of X_(v)O_(w), wherein X represents an element from thefamily consisting of Hf and Zr, and wherein the subscripts v and w havenon-zero values that form a stable compound, and (c) has a thicknessbetween 20 and 65 angstroms.
 22. The memory cell of claim 21, whereinthe band gap is smaller than 1.12 electron volts.
 23. The memory cell ofclaim 21, wherein the diode comprises one or more of germanium (Ge) anda silicon germanium alloy (Si_(xGe) _(1-x)).
 24. The memory cell ofclaim 21, wherein the dielectric material layer comprises HfO₂ or ZrO₂.25. The memory cell of claim 21, wherein the memory cell is adapted tobe programmed with a voltage less than about 5 volts.
 26. The memorycell of claim 21, wherein the diode comprises re-crystallized material.27. The memory cell of claim 21, wherein the diode is formed fromdeposited material.
 28. The memory cell of claim 21, wherein the diodeis adapted to be read using a bias voltage less than about 2 volts. 29.The memory cell of claim 21, wherein the memory cell comprises an arrayof such memory cells.
 30. The memory cell of claim 29, wherein the arrayof memory cells comprises a monolithic 3-dimensional array.